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Hydrodesulfurization catalyst for diesel oil and hydrotreating method for diesel oil

a diesel oil and hydrotreating technology, applied in the direction of organic compounds/hydrides/coordination complex catalysts, physical/chemical process catalysts, chemical apparatuses, etc., can solve the problems of sulfur content, diesel oil sulfur content may adversely affect the durability of after-treatment apparatuses, etc., to achieve low sulfur content, high desulfurization activity, and significant reduction of sulfur content in diesel oil fractions

Active Publication Date: 2018-06-05
COSMO OIL CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Benefits of technology

The catalyst achieves high desulfurization activity and maintains performance under relatively mild conditions, reducing sulfur content in diesel oil effectively and allowing for easy supply of low-sulfur diesel oil without significant modifications to conventional apparatuses.

Problems solved by technology

Particularly, since there is a concern that a sulfur content in diesel oil may adversely influence the durability of after-treatment apparatuses expected as countermeasures against exhaust gas, such as oxidation catalysts, nitrogen oxide (NOx) reduction catalysts, and continuous regenerating type diesel exhaust particle removing filters, it is required to reduce the sulfur content in diesel oil.

Method used

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Examples

Experimental program
Comparison scheme
Effect test

preparation example 1

[0149]Preparation of Zeolite

[0150]Zeolite 1 used in the following Examples and the like was prepared in the following manner.

[0151]29 g of sodium aluminate containing 17.0% by mass of Na2O and 22.0% by mass of Al2O3 was added to 230 g of an aqueous solution of 21.7% by mass of sodium hydroxide in an autoclave vessel while stirring. The sodium aluminate-added solution was added into 232 g of No. 3 water glass having a SiO2 concentration of 24% by mass while stirring. The mixture was sufficiently stirred and then heated and matured at 95° C. for 12 hours. After maturing was completed, cooling was carried out so that the temperature reached 70° C. or lower. Then, synthesized products were removed and filtering, washing, and drying were carried out to prepare Na—Y type seed crystals. The composition of the obtained seed crystal was Na2O / Al2O3=16, SiO2 / Al2O3=15, H2O / Al2O3=330 at an oxide molar ratio.

[0152]Next, 220 g of a sodium silicate solution having a SiO2 concentration of 29% by mas...

example 1

[0159]3.4 g of Zeolite 1 and 218.8 g of alumina hydrate were kneaded, extrusion-molded and then calcined at 600° C. for 2 hours to obtain a zeolite-alumina composite support in the form of cylindrical moldings having a diameter of 1 / 16 inch (zeolite / alumina mass ratio=6 / 94, pore volume=0.82 ml / g, specific surface area=321 m2 / g, average pore diameter=8.9 nm).

[0160]Separately, 17.09 g of cobaltous citrate and 3.72 g of phosphoric acid (85% aqueous solution) were added to 43.4 g of ion exchange water followed by heating to 80° C. and stirring for 10 minutes. Next, 29.34 g of molybdophosphoric acid was added thereto and dissolved, followed by stirring at the same temperature for 15 minutes to prepare a solution for impregnation (impregnating solution).

[0161]Into an eggplant type flask was introduced 50.0 g of the above zeolite-alumina composite support. The entire amount of the above impregnating solution was added thereto with a pipet and the support was immersed in the solution at abo...

example 2

[0163]A zeolite-alumina composite support (zeolite / alumina mass ratio=6 / 94, pore volume=0.79 ml / g, specific surface area=329 m2 / g, average pore diameter=8.8 nm) having the same shape as in Example 1 was obtained in the same manner as in Example 1 except that Zeolite 1 of Example 1 was changed to Zeolite 2. Into an eggplant type flask was introduced 50 g of the zeolite-alumina composite support, the entire amount of the same impregnating solution as in Example 1 was added thereto and the support was immersed in the solution in the same manner as in Example 1. Then, the support was air-dried, dried, and calcined in the same manner as in Example 1 to obtain Catalyst B.

[0164]In Catalyst B, the specific surface area was 155 m2 / g, the pore volume was 0.41 ml / g and the average pore diameter was 12.5 nm.

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Abstract

A hydrodesulfurization catalyst supports one or more metals selected from elements in Group 6 of the Periodic table, one or more metals selected from elements in Group 9 or Group 10 of the same, phosphorus, and an organic acid on a composite oxide support having a specific content of both alumina and HY zeolite having a specific crystallite size. The catalyst includes 10% to 40% by mass of the Group 6 metal, 1% to 15% by mass of the Group 9 or Group 10 metal, and 1.5% to 8% by mass of phosphorus in terms of an oxide based on the catalyst. The catalyst includes 0.8% to 7% by mass of carbon derived from an organic acid and for 1 mole of the Group 9 or Group 10 element metal in terms of an element based on the catalyst, and includes 0.2 to 1.2 moles of the organic acid.

Description

CROSS-REFERENCE TO RELATED APPLICATION[0001]This application is a Section 371 of International Application No. PCT / JP2014 / 055266, filed Mar. 3, 2014, which was published in the Japanese language on Oct. 2, 2014, under International Publication No. WO 2014 / 156486 A1, and the disclosure of which is incorporated herein by reference.TECHNICAL FIELD[0002]The present invention relates to a hydrodesulfurization catalyst for diesel oil and a hydrotreating method for diesel oil using the same. Specifically, the present invention relates to a hydrodesulfurization catalyst having excellent activity capable of reducing a sulfur content and a nitrogen content in diesel oil compared to the case of using this type of catalyst of the related art.[0003]Priority is claimed on Japanese Patent Application No. 2013-062267, filed Mar. 25, 2013, the content of which is incorporated herein by reference.BACKGROUND ART[0004]In recent years, there is a global tendency toward stricter quality regulation values...

Claims

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Application Information

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Patent Type & Authority Patents(United States)
IPC IPC(8): C10G45/12B01J29/16B01J31/34B01J35/10
CPCB01J29/166B01J31/34B01J35/1019B01J35/1038B01J35/1061C10G45/12B01J35/1042B01J2229/20B01J2229/186B01J31/04B01J2231/645B01J2231/70B01J35/635B01J35/633B01J35/647B01J35/615
Inventor NAKAJIMA, NOBUMASAHASHIMOTO, MINORUYOSHINARI, MOTOKIFUJIKAWA, TAKASHI
Owner COSMO OIL CO LTD
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